Metallized acid polyazo dyes



Patented Sept. 3, 1940 I I UN 1 T E 21 stares;

AE 1 T 2,213,647 METALL'IZED ACID POLYAZO DYES Moses L. Crossley, Plainfield, and Lincoln M. Shafer, Upper Montclair, N. .L, assignors, by mesne assignments, to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application June 26, 1937, Serial No. 150,540

Claims. (01. 260-145) compound of a polyazo dye having a middle com-.

ing a metallizable group such as a hydroxyl or.

carboxyl group ortho to the azo group and at least one end component containing a SOIUblIiZ-r ing group. The dyes may be represented by the following general structural formula:

in which R1 is a radical of the naphthalene series and R, R2 and R3 are aryl compounds and the hydroxy groups on R1 are ortho to the two azo groups, at least one of the radicals R andRz having a metallizable group such as a hydroxyl or carboxyl ortho to the azo group connecting the radical to R and at least one of the groups R and R3 having a solubilizing group.

In carrying out the present invention, the polyazo dyes are metallized with copper or combinations of copper and other metals such as copper-chromium, copper-vanadium, copperzinc, copper-iron, and the like. The combina- 35 tions of copper with the other metals react'with the dye to produce products which are not identical with the mixture of the products obtained by treating portions of the dye with separate metals. The metallic combination or complex enters into the dye molecule in some manner metal. The, precise form of chemical combination has not as yet been determined.

The ratio of the metal or metal complex to the dye may vary within wide limits and may depend 45 on the nature of the metal and the number and nature of the metallizable groups in the dye until coupling is complete.

which is difierent from the reaction of a single throughout the coupling. The mixture is then made acid to Congo and the dye salted out with ticular process of producing the dyes. Normally they will be prepared by coupling the dihydroxy compound with a diazo compound and a diazoazo compound. Of course, the polyazo dyes may be produced by successive couplings of diazoamino compounds which are then rediazotized and further coupled. The end components may be the same or different.

Metallization is effected in the normal manner, for example, by refluxing an aqueous solution of the dye with copper salts or other suitable compounds of copper or mixtures with other metal salts or compounds.

In general, the new dyes are dark colored powders which are quite soluble in water and are capable of producing valuable colors of varied tones when dyed from an acid bath on wool, silk, leather and furs. The dyes show good to excellent fastness to light, washing, fulling, acid, alkalies and sea water. The degree of fastness will vary with the particular dyes and with the metals used.

The invention will be described in detail in the following examples but it should be understood that the invention is not limited to the details therein set forth.

Example 1 160 parts of 1-5 dihydroxy naphthalene is suspended in 2500 parts of water and 400 parts of soda ash is added. The solution is cooled with ice to 510 C. and then mixed with the diazo product obtained from 189 parts of 2 amino phenol 4 sulfonic acid. The mixture is stirred Then the diazo compound obtained from 307 parts of the dye produced by coupling para amino salicyclic acid with alpha naphthylamine in acid solution is added. Sufficient sodium carbonate to have thereaction alkaline throughout the coupling is added. Then the mixture is stirred until the second coupling is complete. The reaction must be alkaline may be substituted for copper and similar metallized products obtained.

The formula for the dye prior to metallization is as follows:

OH OH S OaNa H Example 2 Dissolve one molecular weight of the dye shown in the formula below in 8 to 10 times its weight of water. Add 1 molecular weights of N0I S0211 The following table illustrates further dyes which can be produced according tothe present invention: Y

7 Table of types of dye Color produced by First component Middle component Second component metallized product, Ou

0H 0H NH, OINQNHQ [D SOBH Black. O: H

0 4 on NB:

H0 Green.

N=N-(|3-(|3CH: H

EEO- & one: 45 N V..-- S -xm" N=NC-CGH; OH HgN HO- OH Yellowish brown.

\N/ HOaS H N=NC-CCH; OH NH:

80M 1 NO; Blue.

0H 0H N111 Blue. H N= 7 Color produced by Fxrst component Mlddle component second component metallized product, Cu

5. OH OH NH: OH NH:

N=N Blue 1 H SOxH N0:

S 03H OH OH NHa NHa 803B: Reddlsh blue.

HOaS

N=N S0511 N=N 0H 7 HO 01 NHa OH OzH H N=N-Q G N=N(IJfiCH; men

EEO- N NH; 0H NH: OxH

OH CH;

CH Reddish blu e.

OH H N=N Ho NHaoH 0 0H Reddish brown.

S 03H N02 =N 60 on 2 0H NH:

OEN NH:

Bl ;0m ;11

N: 55 OH HOIS SOaH NH; OH NH:

CHHO

R H ed 08H 0H 0H NH:

NH: [1; S05 70 0H 1: 1 H Dar blue & SOaH This application is in part a continuation of our copending application Serial No. 676,318, filed June 17, 1933 now Patent 2,136,650 of November 15, 1938.

We claim:

1. Complex copper compounds of azo dyes, the azo dye component of which has the following formula:

in which the radicals R, R2 and R3 are aryl radicals, R1 is a naphthyl radical having the hydroxyls ortho to the two azo groups, at least one of the radicals R and R2 having a metallizable group ortho to the azo group connecting the radical to R1, and at least oneof the radicals R and R3 containing a solubilizinggroup.

2. A complex copper compound of the dye according to claim 1 in which both R and R2 contain a metallizable group ortho to the azo groups connecting the radicals to the dihydroxynaphthalene radical.

3. A complex copper compound of a dye according to claim 1 in which R3 is an aryl azoaryl radical.

" group connecting it to R2.

5. A complex copper compound of the azo dye having the following formula SOaH N=N SOaH MOSES L. CROSSLEY. LINCOLN M. SHAFER.

Certificate of Correction Patent N 0. 2,213,647. September 3, 1940.

MOSES L. OROSSLEY ET AL. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 4, second column, line 21, claim 5, for that portion of the formula reading N=N om N=N read and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 8th day of October, A. D. 1940.

[SEAL] HENRY VAN ARSDALE,

Acting Commissioner of Patents. 

